WO2020250594A1 - Composition de résine, fibre optique et procédé de fabrication de fibre optique - Google Patents

Composition de résine, fibre optique et procédé de fabrication de fibre optique Download PDF

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Publication number
WO2020250594A1
WO2020250594A1 PCT/JP2020/018347 JP2020018347W WO2020250594A1 WO 2020250594 A1 WO2020250594 A1 WO 2020250594A1 JP 2020018347 W JP2020018347 W JP 2020018347W WO 2020250594 A1 WO2020250594 A1 WO 2020250594A1
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meth
acrylate
resin composition
resin layer
optical fiber
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PCT/JP2020/018347
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English (en)
Japanese (ja)
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勝史 浜窪
一之 相馬
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住友電気工業株式会社
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Priority to JP2021525941A priority Critical patent/JPWO2020250594A1/ja
Priority to EP20822509.4A priority patent/EP3984973A4/fr
Priority to CN202080041083.2A priority patent/CN113966371A/zh
Priority to US17/269,746 priority patent/US20210198517A1/en
Publication of WO2020250594A1 publication Critical patent/WO2020250594A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/1065—Multiple coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/104—Coating to obtain optical fibres
    • C03C25/105—Organic claddings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/285—Acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/62—Surface treatment of fibres or filaments made from glass, minerals or slags by application of electric or wave energy; by particle radiation or ion implantation
    • C03C25/6206—Electromagnetic waves
    • C03C25/6226—Ultraviolet
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02395—Glass optical fibre with a protective coating, e.g. two layer polymer coating deposited directly on a silica cladding surface during fibre manufacture
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/02—Pure silica glass, e.g. pure fused quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/08—Doped silica-based glasses containing boron or halide
    • C03C2201/12—Doped silica-based glasses containing boron or halide containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/31—Doped silica-based glasses containing metals containing germanium

Definitions

  • the present disclosure relates to resin compositions, optical fibers and methods for producing optical fibers.
  • This application claims priority based on Japanese Application No. 2019-11920 filed on June 14, 2019, and incorporates all the contents described in the Japanese application.
  • an optical fiber has a coating resin layer for protecting a glass fiber which is an optical transmitter.
  • the coating resin layer generally includes a primary resin layer and a secondary resin layer.
  • the optical fiber is required to have excellent lateral pressure characteristics.
  • Patent Document 1 it is studied to reduce the bending loss of an optical fiber by increasing the Young's modulus of the secondary resin layer (second coating).
  • the resin composition according to one aspect of the present disclosure contains a base resin containing an oligomer, a monomer and a photopolymerization initiator, and hydrophobic inorganic oxide particles, and the oligomers are urethane (meth) acrylate and epoxy (meth). )
  • the mass ratio of the content of urethane (meth) acrylate to the content of epoxy (meth) acrylate containing acrylate is 0.25 or more.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment.
  • An object of the present disclosure is to provide a resin composition capable of efficiently producing an optical fiber having excellent lateral pressure resistance characteristics, and an optical fiber provided with a secondary resin layer formed from the resin composition.
  • the resin composition according to one aspect of the present disclosure contains a base resin containing an oligomer, a monomer and a photopolymerization initiator, and hydrophobic inorganic oxide particles, and the oligomers are urethane (meth) acrylate and epoxy (meth).
  • the mass ratio of the content of urethane (meth) acrylate to the content of epoxy (meth) acrylate containing acrylate is 0.25 or more.
  • Such a resin composition can reduce the heat of reaction at the time of curing.
  • an ultraviolet curable resin composition for coating an optical fiber an optical fiber having excellent lateral pressure resistance can be produced efficiently.
  • the amount of heat of reaction when the above resin composition is irradiated with ultraviolet rays at an irradiation intensity of 30 mW / cm 2 for 300 seconds is 100 J / g. It may be 275 J / g or less.
  • the above-mentioned monomer may contain a polyfunctional monomer having two or more polymerizable groups.
  • the inorganic oxide particles are more than the group consisting of silicon dioxide, zirconium dioxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide and zinc oxide. It may be a particle containing at least one selected. Since the reaction heat and Young's modulus can be more easily adjusted, the content of the inorganic oxide particles may be 1% by mass or more and 60% by mass or less based on the total amount of the oligomers, monomers and inorganic oxide particles.
  • the optical fiber according to one aspect of the present disclosure includes a glass fiber including a core and a clad, a primary resin layer that is in contact with the glass fiber and coats the glass fiber, and a secondary resin layer that coats the primary resin layer.
  • the resin layer contains a cured product of the above resin composition. Thereby, the lateral pressure characteristic of the optical fiber can be improved.
  • the Young's modulus of the secondary resin layer may be 1200 MPa or more and 3500 MPa or less at 23 ° C. because the lateral pressure characteristics of the optical fiber can be easily improved.
  • the method for producing an optical fiber according to one aspect of the present disclosure includes a coating step of applying the above resin composition to the outer periphery of a glass fiber composed of a core and a clad, and a resin composition by irradiating ultraviolet rays after the coating step. Includes a curing step of curing an object. As a result, an optical fiber having excellent lateral pressure resistance can be produced with high production efficiency.
  • the resin composition according to the present embodiment contains a base resin containing an oligomer, a monomer and a photopolymerization initiator, and hydrophobic inorganic oxide particles.
  • the oligomer according to the present embodiment includes urethane (meth) acrylate and epoxy (meth) acrylate.
  • the mass ratio (UA / EA) of the content of urethane (meth) acrylate (UA) to the content of epoxy (meth) acrylate (EA) is 0.25 or more.
  • the UA / EA is preferably 0.45 or more, more preferably 0.5 or more, and even more preferably 0.7 or more.
  • the upper limit of UA / EA may be 5.0 or less, 4.0 or less, or 3.5 or less.
  • the urethane (meth) acrylate an oligomer obtained by reacting a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound can be used.
  • the (meth) acrylate means an acrylate or a methacrylate corresponding thereto. The same applies to (meth) acrylic acid.
  • Examples of the polyol compound include polytetramethylene glycol, polypropylene glycol and bisphenol A / ethylene oxide-added diol.
  • Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane 4,4'-diisocyanate.
  • Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. Examples thereof include 2-hydroxypropyl (meth) acrylate and tripropylene glycol mono (meth) acrylate.
  • the number average molecular weight (Mn) of the polyol compound is preferably 300 or more and 3000 or less, more preferably 400 or more and 2500 or less, and further preferably 500 or more and 2000 or less.
  • An organic tin compound is generally used as a catalyst for synthesizing urethane (meth) acrylate.
  • organotin compound examples include dibutyltin dilaurate, dibutyltin diacetate, dibutyltinmalate, dibutyltinbis (2-ethylhexyl mercaptoacetate), dibutyltinbis (isooctyl mercaptoacetate) and dibutyltin oxide. From the viewpoint of easy availability or catalytic performance, it is preferable to use dibutyltin dilaurate or dibutyltin diacetate as the catalyst.
  • a lower alcohol having 5 or less carbon atoms may be used when synthesizing urethane (meth) acrylate.
  • the lower alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, and the like. Examples thereof include 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol and 2,2-dimethyl-1-propanol.
  • an oligomer obtained by reacting an epoxy resin having two or more glycidyl groups with a compound having a (meth) acryloyl group can be used.
  • the monomer at least one selected from the group consisting of a monofunctional monomer having one polymerizable group and a polyfunctional monomer having two or more polymerizable groups can be used. Two or more kinds of monomers may be mixed and used.
  • Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, and tert-butyl (meth) acrylate.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate.
  • Di (meth) acrylate of alkylene oxide adduct of bisphenol A tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,16-hexadecane EO addition of diol di (meth) acrylate, 1,20-eicosane diol di (meth) acrylate, isopentyl diol di (meth) acrylate, 3-ethyl-1,8-octane diol di (meth) acrylate, bisphenol A
  • the monomer preferably contains a polyfunctional monomer, and more preferably contains a monomer having two polymerizable groups.
  • the photopolymerization initiator it can be appropriately selected from known radical photopolymerization initiators and used.
  • the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone (Omnirad 184, manufactured by IGM Resins), 2,2-dimethoxy-2-phenylacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-.
  • Methylpropan-1-one bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -On (Omnirad 907, manufactured by IGM Resins), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resins) and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819) , IGM Resins).
  • the content of the photopolymerization initiator is preferably 0.2% by mass or more and 6.0% by mass or less, preferably 0.4% by mass, based on the total amount of oligomers and monomers. More than 3.0% by mass is more preferable, and 0.6% by mass or more and 2.0% by mass or less is further preferable.
  • the resin composition may further contain a silane coupling agent, a leveling agent, an antifoaming agent, an antioxidant, a sensitizer and the like.
  • the silane coupling agent is not particularly limited as long as it does not interfere with the curing of the resin composition.
  • examples of the silane coupling agent include tetramethyl silicate, tetraethyl silicate, mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxy-ethoxy) silane, and ⁇ - (3,4-epylcyclohexyl).
  • -Ethyltrimethoxysilane dimethoxydimethylsilane, diethoxydimethylsilane, 3-acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyl Trimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -Chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, bis- [3- (triethoxysilyl) prop
  • the surface of the inorganic oxide particles according to the present embodiment is hydrophobically treated.
  • the hydrophobic treatment according to the present embodiment means that a hydrophobic group is introduced on the surface of the inorganic oxide particles.
  • the inorganic oxide particles into which a hydrophobic group has been introduced are excellent in dispersibility in the resin composition.
  • the hydrophobic group is a reactive group such as a (meth) acryloyl group or a vinyl group, or a non-reactive group such as an aliphatic hydrocarbon group (for example, an alkyl group) or an aromatic hydrocarbon group (for example, a phenyl group). It may be a group. When the inorganic oxide particles have a reactive group, it becomes easy to form a resin layer having a high Young's modulus.
  • the inorganic oxide particles according to this embodiment are dispersed in a dispersion medium.
  • the inorganic oxide particles can be uniformly dispersed in the resin composition, and the storage stability of the resin composition can be improved.
  • the dispersion medium is not particularly limited as long as it does not inhibit the curing of the resin composition.
  • the dispersion medium may be reactive or non-reactive.
  • a monomer such as a (meth) acryloyl compound or an epoxy compound
  • examples of the (meth) acryloyl compound include 1,6-hexanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, polyethylene glycol di (meth) acrylate, and PO-modified bisphenol A di (meth) acrylate. Examples thereof include polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate.
  • the (meth) acryloyl compound the compound exemplified by the above-mentioned monomer may be used.
  • a ketone solvent such as methyl ethyl ketone (MEK), an alcohol solvent such as methanol (methanol), or an ester solvent such as propylene glycol monomethyl ether acetate (PGMEA) may be used.
  • MEK methyl ethyl ketone
  • methanol methanol
  • PMEA propylene glycol monomethyl ether acetate
  • the base resin and the inorganic oxide particles dispersed in the dispersion medium may be mixed, and then a part of the dispersion medium may be removed to prepare a resin composition.
  • an optical microscope magnification of about 100 times
  • the inorganic oxide particles dispersed in the dispersion medium exist in a dispersed state in the resin layer even after the resin composition is cured.
  • a reactive dispersion medium used, the inorganic oxide particles are mixed with the resin composition together with the dispersion medium and incorporated into the resin layer while maintaining the dispersed state.
  • a non-reactive dispersion medium used, at least a part of the dispersion medium volatilizes from the resin composition and disappears, but the inorganic oxide particles remain in the resin composition in a dispersed state and the cured resin layer. Also exists in a dispersed state.
  • the inorganic oxide particles existing in the resin layer are observed in a state in which the primary particles are dispersed when observed with an electron microscope.
  • the inorganic oxide particles are silicon dioxide (silica), zirconium dioxide (zirconia), aluminum oxide (alumina), magnesium oxide (alumina) because they have excellent dispersibility in the resin composition and easily form a tough resin layer. It is preferably at least one species from the group consisting of magnesia), titanium oxide (titania), tin oxide and zinc oxide. Hydrophobic silica particles are used as the inorganic oxide particles according to the present embodiment from the viewpoints of excellent low cost, easy surface treatment, ultraviolet transmission, and easy to impart appropriate hardness to the resin layer. It is more preferable to use it.
  • the average primary particle size of the inorganic oxide particles may be 500 nm or less, preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less.
  • the average primary particle size of the inorganic oxide particles is preferably 5 nm or more, more preferably 10 nm or more.
  • the average primary particle size can be measured by, for example, image analysis of electron micrographs, a light scattering method, a BET method, or the like.
  • the dispersion medium in which the primary particles of the inorganic oxide are dispersed looks transparent visually when the particle size of the primary particles is small. When the particle size of the primary particles is relatively large (40 nm or more), the dispersion medium in which the primary particles are dispersed appears cloudy, but no sediment is observed.
  • the content of the inorganic oxide particles is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 55% by mass or less, and 10% by mass or more and 50% or more, based on the total amount of oligomers, monomers and inorganic oxide particles. More preferably, it is by mass or less.
  • the content of the inorganic oxide particles is 1% by mass or more, the Young's modulus of the resin layer can be easily increased.
  • the content of the inorganic oxide particles is 60% by mass or less, the reaction heat of the resin composition can be easily reduced.
  • the amount of heat of reaction when the resin composition according to the present embodiment is irradiated with ultraviolet rays at an intensity of 30 mW / cm 2 for 300 seconds is determined. It is preferably 100 J / g or more and 275 J / g or less, more preferably 110 J / g or more and 265 J / g or less, and further preferably 120 J / g or more and 260 J / g or less.
  • the reaction calorific value of the resin composition can be measured using a differential scanning calorimeter (ultraviolet irradiation DSC) equipped with an ultraviolet irradiation device.
  • the resin composition according to this embodiment can be suitably used as a secondary coating material for an optical fiber.
  • the resin composition according to the present embodiment for the secondary resin layer it is possible to suppress the generation of voids when producing an optical fiber by increasing the linear velocity, and to produce an optical fiber having excellent lateral pressure characteristics. ..
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical fiber according to the present embodiment.
  • the optical fiber 10 includes a glass fiber 13 including a core 11 and a clad 12, and a coating resin layer 16 including a primary resin layer 14 and a secondary resin layer 15 provided on the outer periphery of the glass fiber 13.
  • the clad 12 surrounds the core 11.
  • the core 11 and the clad 12 mainly contain glass such as quartz glass.
  • glass such as quartz glass.
  • quartz glass or pure quartz glass to which germanium is added can be used for the core 11, and pure quartz glass or pure quartz glass or pure quartz glass can be used for the clad 12.
  • Fused quartz glass to which fluorine has been added can be used.
  • the outer diameter (D2) of the glass fiber 13 is about 100 ⁇ m to 125 ⁇ m, and the diameter (D1) of the core 11 constituting the glass fiber 13 is about 7 ⁇ m to 15 ⁇ m.
  • the thickness of the coating resin layer 16 is usually about 22 ⁇ m to 70 ⁇ m.
  • the thickness of each of the primary resin layer 14 and the secondary resin layer 15 may be about 5 ⁇ m to 50 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 10 ⁇ m to 50 ⁇ m.
  • the thickness of the primary resin layer 14 may be 35 ⁇ m, and the thickness of the secondary resin layer 15 may be 25 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 245 ⁇ m to 265 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 10 ⁇ m to 38 ⁇ m.
  • the thickness of the primary resin layer 14 may be 25 ⁇ m, and the thickness of the secondary resin layer 15 may be 10 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 179 ⁇ m to 221 ⁇ m.
  • the thickness of each layer of the primary resin layer 14 and the secondary resin layer 15 is about 5 ⁇ m to 32 ⁇ m.
  • the thickness of the primary resin layer 14 may be 25 ⁇ m, and the thickness of the secondary resin layer 15 may be 10 ⁇ m.
  • the outer diameter of the optical fiber 10 may be about 144 ⁇ m to 174 ⁇ m.
  • the resin composition according to the present embodiment By applying the resin composition according to the present embodiment to the secondary resin layer, it is possible to produce an optical fiber having a high Young's modulus and excellent lateral pressure characteristics.
  • the method for producing an optical fiber according to the present embodiment is a coating step of applying the above resin composition to the outer periphery of a glass fiber composed of a core and a clad, and a coating step of applying ultraviolet rays after the coating step to apply the resin composition. Includes a curing step of curing.
  • the Young's modulus of the secondary resin layer is preferably 1200 MPa or more and 3500 MPa or less at 23 ° C., more preferably 1200 MPa or more and 3300 MPa or less, and further preferably 1300 MPa or more and 3000 MPa or less.
  • the Young's modulus of the secondary resin layer is 1200 MPa or more, the lateral pressure characteristics of the optical fiber are easily improved, and when it is 3500 MPa or less, appropriate toughness can be imparted to the secondary resin layer, so that cracks or the like occur in the secondary resin layer. It becomes difficult.
  • the primary resin layer 14 can be formed by curing, for example, a resin composition containing a urethane (meth) acrylate oligomer, a monomer, a photopolymerization initiator and a silane coupling agent.
  • a resin composition for the primary resin layer a conventionally known technique can be used.
  • the urethane (meth) acrylate oligomer, monomer, photopolymerization initiator and silane coupling agent may be appropriately selected from the compounds exemplified in the above base resin.
  • the resin composition forming the primary resin layer has a composition different from that of the base resin forming the secondary resin layer.
  • the Young's modulus of the primary resin layer is preferably 0.04 MPa or more and 1.0 MPa or less, and 0.05 MPa or more and 0.9 MPa or less at 23 ° C. Is more preferable, and 0.05 MPa or more and 0.8 MPa or less is further preferable.
  • the linear speed when manufacturing the optical fiber may be 500 m / min or more.
  • the linear velocity is preferably 1000 m / min or more, more preferably 1500 m / min or more, and further preferably 2000 m / min or more.
  • Resin composition for secondary resin layer (Oligomer)
  • a urethane acrylate oligomer (UA) obtained by reacting polypropylene glycol, 2,4-tolylene diisocyanate and hydroxyethyl acrylate having a molecular weight of 600 and an epoxy acrylate oligomer (EA) were prepared.
  • TPGDA tripropylene glycol diacrylate
  • Photopolymerization initiator As a photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone (Omnirad 184) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO) were prepared.
  • Inorganic oxide particles As the inorganic oxide particles, a silica sol having a methacryloyl group and hydrophobic silica particles having an average primary particle size of 10 to 15 nm dispersed in MEK was prepared.
  • the numerical values of the oligomer, the monomer and the photopolymerization initiator are the contents based on the total amount of the oligomer and the monomer
  • the numerical value of the silica particles is based on the total amount of the monomer, the oligomer and the silica particles. Content.
  • the heat of reaction of the resin composition for the secondary resin layer was measured by UV irradiation DSC. The measurement was carried out under the following conditions by putting about 3 mg of the resin composition in an aluminum container having a diameter of 5 mm.
  • Differential scanning calorimetry Q100 (manufactured by TA Instruments)
  • Data processing Universal Analysis 2000 (manufactured by TA Instruments)
  • Atmosphere Nitrogen (50 mL / min) Temperature: 25 ° C
  • Ultraviolet irradiation device OmniCure S2000 (manufactured by Uvix)
  • Light source High-pressure mercury lamp (all wavelengths)
  • Irradiation intensity 30 mW / cm 2
  • Irradiation time 300 seconds (light irradiation starts 1 minute after the start of measurement)
  • a urethane acrylate oligomer obtained by reacting polypropylene glycol, isophorone diisocyanate, hydroxyethyl acrylate and methanol having a molecular weight of 4000 was prepared.
  • this urethane acrylate oligomer 75 parts by mass of this urethane acrylate oligomer, 12 parts by mass of nonylphenol EO modified acrylate, 6 parts by mass of N-vinylcaprolactam, 2 parts by mass of 1,6-hexanediol diacrylate, 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide , And 1 part by mass of 3-mercaptopropyltrimethoxysilane were mixed to obtain a resin composition for the primary resin layer.
  • a resin composition for a primary resin layer and a resin composition of Example or Comparative Example are applied to the outer periphery of a glass fiber having a diameter of 125 ⁇ m composed of a core and a clad for a secondary resin layer, and then irradiated with ultraviolet rays.
  • the resin composition was cured to form a primary resin layer having a thickness of 35 ⁇ m and a secondary resin layer having a thickness of 25 ⁇ m on the outer periphery thereof to prepare an optical fiber.
  • the optical fiber was manufactured by changing the linear velocity to 500 m / min, 1000 m / min, and 2000 m / min, respectively.
  • the applicability of the resin composition was evaluated by confirming the presence or absence of disconnection and the presence or absence of cracks in the resin layer of the optical fiber produced by changing the linear velocity. The case where there was no disconnection or crack in the resin layer was evaluated as "A”, the case where there was disconnection and there was no crack in the resin layer was evaluated as "B”, and the case where there was disconnection and the resin layer was cracked was evaluated as "C”.
  • the following evaluation was performed using an optical fiber manufactured at a linear speed of 2000 m / min.
  • the Young's modulus of the primary resin layer was measured by the Pullout Modulus (POM) method at 23 ° C. Two points of the optical fiber are fixed by two chuck devices, the coating resin layer (primary resin layer and secondary resin layer) portion between the two chuck devices is removed, then one chuck device is fixed and the other. The chuck device was gently moved in the opposite direction of the fixed chuck device. The length of the part sandwiched between the moving chuck devices in the optical fiber is L, the moving amount of the chuck is Z, the outer diameter of the primary resin layer is Dp, the outer diameter of the glass fiber is Df, and the Poisson's ratio of the primary resin layer is n.
  • L The length of the part sandwiched between the moving chuck devices in the optical fiber
  • the moving amount of the chuck is Z
  • the outer diameter of the primary resin layer is Dp
  • the outer diameter of the glass fiber is Df
  • the Poisson's ratio of the primary resin layer is n.
  • the Young ratio of the primary resin layer was obtained from the following formula.
  • the Young's modulus of the primary resin layer was 0.2 MPa.
  • Young's modulus (MPa) ((1 + n) W / ⁇ LZ) ⁇ ln (Dp / Df)
  • the Young's modulus of the secondary resin layer is tensioned in an environment of 23 ⁇ 2 ° C. and 50 ⁇ 10% RH using a pipe-shaped coated resin layer (length: 50 mm or more) obtained by extracting the glass fiber from the optical fiber. A test (distance between marked lines: 25 mm) was performed, and the value was determined from the 2.5% score line value.
  • a 10 m optical fiber was stored at 85 ° C. under a humidity of 85% for 120 days, then placed at ⁇ 40 ° C. for 16 hours, and the presence or absence of voids having a diameter of 10 ⁇ m or more was observed under a microscope.
  • the case where the number of voids per 1 m of the optical fiber was less than 1 was evaluated as "A”
  • the case where the number of voids was 1 to 2 was evaluated as "B”
  • the case where the number of voids exceeded 2 was evaluated as "C”. ..
  • the transmission loss of light having a wavelength of 1550 nm when an optical fiber was wound in a single layer on a bobbin having a diameter of 280 mm covered with sandpaper was measured by an OTDR (Optical Time Domain Reflectometer) method. Further, the transmission loss of light having a wavelength of 1550 nm when the optical fiber was wound in a single layer on a bobbin having a diameter of 280 mm without sandpaper was measured by the OTDR method.
  • the difference in the measured transmission losses was obtained, and the case where the transmission loss difference was 0.6 dB / km or less was evaluated as the lateral pressure characteristic "A", and the case where the transmission loss difference was more than 0.6 dB / km was evaluated as the lateral pressure characteristic "B".
  • the resin composition containing hydrophobic silica particles and having a UA / EA ratio of 0.25 or more has a small reaction calorific value of 275 J / g or less, and the coating property of the resin composition It can be confirmed that the voids in the optical fiber can be reduced. That is, by using the resin composition according to the present disclosure as an ultraviolet curable resin composition for coating an optical fiber, an optical fiber having excellent lateral pressure resistance can be produced efficiently.

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Abstract

La présente invention concerne une composition de résine pour recouvrir une fibre optique qui comprend une résine de base comprenant un oligomère, un monomère et un initiateur de photopolymérisation et des particules hydrophobes d'oxyde inorganique, l'oligomère comprenant du (méth)acrylate d'uréthane et du (méth)acrylate d'époxy, et le rapport de la teneur en (méth)acrylate d'uréthane à la teneur en (méth)acrylate d'époxy étant supérieur ou égal à 0,25 en masse.
PCT/JP2020/018347 2019-06-14 2020-04-30 Composition de résine, fibre optique et procédé de fabrication de fibre optique WO2020250594A1 (fr)

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JP2021525941A JPWO2020250594A1 (fr) 2019-06-14 2020-04-30
EP20822509.4A EP3984973A4 (fr) 2019-06-14 2020-04-30 Composition de résine, fibre optique et procédé de fabrication de fibre optique
CN202080041083.2A CN113966371A (zh) 2019-06-14 2020-04-30 树脂组合物、光纤以及光纤的制造方法
US17/269,746 US20210198517A1 (en) 2019-06-14 2020-04-30 Resin composition, optical fiber, and method for manufacturing optical fiber

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JPWO2020250594A1 (fr) 2020-12-17
CN113966371A (zh) 2022-01-21
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EP3984973A1 (fr) 2022-04-20
EP3984973A4 (fr) 2022-07-27

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